MXPA99003685A - Detergent compositions - Google Patents

Abstract

The present invention relates to detergent compositions or components thereof containing a cationic dye-fixing agent and one or more cationic surfactants of the formula:R1R2R3R4N+ X- in which R1 is a hydroxyalkyl group having no greater than 6 carbon atoms;each of R2 and R3 is independently selected from C1-4alkyl or alkenyl;R4 is a C5-11alkyl or alkenyl;and X- is a counterion.

Description

DETERGENT COMPOSITIONS TECHNICAL FIELD The present invention relates to detergent compositions or components thereof containing cationic surfactant and a colorant fixing agent. Generally, the detergent compositions of the invention are for use in laundry washing processes.

BACUND OF THE INVENTION It is known how to use cationic surfactants in detergent compositions. For example, GB 2040990A discloses granular detergent compositions comprising cationic surfactants. It is also known to incorporate cationic dye fixative polyamine agents in detergent compositions, as described in EP-A-462806. However, formulations containing such polyamines exhibit poor stain removal properties, since they tend to coat the surfaces of the fabric thus trapping any stain on the surface of the fabric. The use of anionic surfactants to solve this problem can promote dye fading. Applicants have found that this problem can be reduced by using a cationic surfactant in combination with cationic dye fixative polyamine agents. Further, it is considered that after the cleavage of any oily dirt caused by the enzyme, the cationic surfactants used in the present invention can complex with the fatty acids and any other negatively charged product produced by the cleavage, increasing their solubility and increasing the removal of dirt from grease and oil and the general cleaning action, before the deposition of the coloring fixing agents. All documents cited in the present description are incorporated herein by reference.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a detergent composition or component thereof comprising: a) a dye fixing cationic agent; and b) a cationic surfactant of formula I: R1R2R3R4N + X " Wherein R1 is a hydroxyalkyl group having not more than 6 carbon atoms; each of R2 and R3 is independently selected from C? -4 alkyl or alkenyl; R4 is an alkyl or alkenyl of C5-? 8; and X "is a counterion.

As used herein, unless otherwise indicated, alkyl or alkenyl may be branched, linear or substituted. The substituents may be, for example, aromatic groups, heterocyclic groups containing one or more N, S, O atoms, or halogen substituents.

DETAILED DESCRIPTION OF THE INVENTION Cationic Surfactant In general, the cationic surfactant is present in the composition or component thereof in an amount of not more than 60% by weight, preferably not more than 10% by weight, preferably in an amount not greater than 4.5% or even 3% by weight. The benefits of the invention are obtained even with very small amounts of the cationic surfactant of formula I. Generally, there will be at least 0.01% by weight, preferably at least 0.05%, or at least 0.1% by weight of the surfactant cationic in the detergent compositions of the invention. Preferably, R1 in the formula I is a hydroxyalkyl group having not more than 6 carbon atoms and preferably the -OH group is separated from the nitrogen atom of the quaternary ammonium by not more than 3 carbon atoms. Preferred R1 groups are -CH2CH2OH, -CH2CH2CH2OH, -CH2CH (CH3) OH and -CH (CH3) CH2OH. Preferred are -CH2CH2OH and -CH2CH2CH2OH, and -CH2CH2OH is particularly preferred. Preferably, R2 and R3 are each selected from ethyl and methyl groups, and preferably both R2 and R3 are methyl groups. Preferred R4 groups have at least 6 or even at least 7 carbon atoms. R4 can have no more than 9 carbon atoms, or even no more than 8 or 7 carbon atoms. Preferred R4 groups are linear alkyl groups. The linear R4 groups that have 8 to 11 carbon atoms are preferred, or from 8 to 10 carbon atoms. Preferably, each of R2 and R3 is selected from C- alkyl and R4 is C6-n alkyl or alkenyl. Although pure or substantially pure cationic compounds are within the scope of this invention, it has been found that mixtures of the cationic surfactants of formula I can be particularly effective, for example, surfactant mixtures in which R4 can be a combination of groups linear alkyl of Ce and C-, or C9 and Cu alkyl groups. According to one aspect of the invention, a mixture of cationic surfactants of formula I is present in the composition, the mixture comprising an alkyl surfactant of shorter chain formula I and an alkyl surfactant of chain formula I long Preferably, the longer chain alkyl cationic surfactant is selected from the surfactants of formula I wherein R 4 is an alkyl group having n carbon atoms, wherein n is from 8 to 11; the shorter chain alkyl surfactant is preferably selected from those of formula I wherein R 4 is an alkyl group having (n-2) carbon atoms. Said cationic surfactant mixtures will generally comprise from 5 to 95% by total weight of cationic surfactant of formula I of a longer alkyl chain length, preferably from 30 to 90%, and preferably at least 50% by weight of mix. Generally, the blends will contain from 5 to 95% by weight, preferably from 5 to 70%, preferably from 35 to 65% by weight, and more preferably at least 40% by weight of cationic surfactant of alkyl chain formula I more short. The invention also comprises a detergent composition comprising cationic dye fixing agent; and a mixture of cationic surfactants of formula I, wherein, in the mixture of cationic surfactants of formula I, at least 10% by weight, preferably at least 20% by weight, have R4 which is alkyl or alkenyl of C5-9. X in formula I can be any counterion that provides electrical neutrality, but is preferably selected from the group consisting of halide, methylsulfate, sulfate and nitrate; preferably it is selected from methyl sulfate, chloride, bromide and iodide. Halide ions, especially chloride, are most preferred.

Dye fixing cationic agent Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid diamine condensates, for example hydrochloride, acetate, methosulfate and oleioldiethyl aminoethylamide benzyl hydrochloride, oleylmethyl diethylenediamine methosulfate, monostearyl ethylenediaminotrimethylammoniomethosulfate, and oxidized products of tertiary amines; derivatives of polymeric alkyldiamines, condensates of polyamine-cyanuric chloride and aminated glyceroldichlorhydrin, as described in EP-A-0462806. Particularly preferred dye fixing agents suitable for use in the process of the invention are cationic species, and examples include aliphatic polyamines such as Indosol E-50 (Sandoz) and Croscolor NOFF, a polymer of dimethyldiallylammonium chloride of molecular weight in the scale from 2,000 to 20,000 (Crosfield). Other cationic dye fixing agents are described in "After-treatments for Improving the Fastness of Dyes on Textile Fibers" by Christopher C. Cook (Rev. Prog. Coloration Vol 12 1982). The amount of dye fixing agent in the detergent compositions of the invention is generally 0.01 to 50% by weight, preferably 0.5 to 30% by weight, and 1 to 20% by weight is most preferred. The weight ratio of dye fixing cationic agent to cationic surfactant is generally from 50: 1 to 1:10, preferably from 20: 1 to 1: 2, preferably from 10: 1 to 3: 2, based on the percentage by weight of active enzyme of the detergent composition.

Additional detergent components The detergent compositions or components thereof according to the invention may also contain additional detergent components. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the cleaning operation in which they are to be used. The compositions or components thereof according to the invention preferably contain one or more additional detergent components selected from additional surfactants, sequestrants, bleaches, bleach precursors, bleach catalysts, organic polymer compounds, additional enzymes, suds suppressors, dispersants. of lime soap, additional suspension and antiredeposition agents for soils, perfumes and corrosion inhibitors.

Additional Surfactant The detergent compositions or components thereof according to the invention preferably contain an additional surfactant selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants, and mixtures thereof. A typical listing of anionic, non-ionic, ampholytic and zwitterionic classes, as well as species of these surfactants, is given in the US patent. No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (Vols. I and II, by Schwartz, Perry and Berch). A listing of suitable cationic surfactants is given in the U.S.A. No. 4,259,217, issued to Murphy on March 31, 1981. When present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic Surfactant The detergent compositions of the invention may also contain an anionic surfactant. Any anionic surfactant useful for detersive purposes is suitable. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred. Other anionic surfactants include isethionates such as acyl isethionates, N-acyltaurates, fatty acid amides of methyltauride, alkylsuccinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated CJ 2-C-8 monoesters), sulfosuccinate diesters (especially saturated and unsaturated Cβ-C di diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids, as well as hydrogenated rosin acids present in tallow oil or derivatives thereof.

Sulphonic Anion Surfactant Anionic sulfate surfactants suitable for use in the compositions of the invention include linear or branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenol ethylene oxide ether sulphates, acyl-N- ( C < RTI ID = 0.0 > C <) < / RTI > -N- (hydroxyalkyl of C- | -C2) -C5-C? -glucamine sulfates 7) and alkylpolysaccharide sulfates such as alkyl polyglucoside sulfates (unsulphated compounds are described herein) non-ionic). The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C9-C22 alkyl sulphates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. Most preferably, the alkyl ethoxy sulfate surfactant is a C 11 -C 18 alkyl sulfate. most preferably of C-11-C15, which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfatelate surfactants. Said mixtures have been described in PCT Application No. WO 93/18124.

Sulfonate Anionic Surfactant The sulfonic anionic surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulphonates. alkyl esters sulfonates, primary or secondary C6-C22 alkan sulfonates, C6-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixture thereof. Particularly preferred compositions of the present invention further comprise an anionic surfactant, selected from alkyl sulfate and / or alkylbenzenesulfonate surfactants of the formulas II and III, respectively: R5S03-M, + (II) R6SO3-M '+ (III) wherein R ^ is a linear or branched alkyl or alkenyl portion having from 9 to 22 carbon atoms, preferably C-? 2 to C? 8 alkyl or as found in secondary alkyl sulfates; R6 is C- | o-Ci6 alkylbenzene > preferably C 1-C 1 -13 alkybenzene; M + and M '+ can vary independently and are selected from alkali metals, alkaline earth metals, alkanolammonium and ammonium. Particularly preferred compositions of the invention comprise both an alkyl sulfate surfactant and an alkyl benzene surfactant, preferably in ratios of II to III from 15: 1 to 1: 2, most preferably from 12: 1 to 2: 1. .

The amounts of the anionic surfactant or of the mixture of more than one anionic surfactant in the preferred composition can be from 1% to 50%; however, preferably the anionic surfactant is present in amounts of 5% to 40% by weight of the composition. The preferred amounts of the alkyl sulfate surfactant of the formula II are 3% by weight. 40%, preferably from 6% to 30% by weight of the detergent composition. Preferred amounts of alkylbenzenesulfonate surfactant of formula III in the detergent composition are at least 1%, preferably at least 2%, or even at least 4% by weight. Preferred amounts of the alkylbenzene sulfonate surfactant are up to 23%, most preferably not more than 20%, more preferably up to 15% or even 10%. The performance benefits obtained when an anionic surfactant is also used in the compositions of the invention, are particularly useful for longer carbon chain length anionic surfactants such as those having a carbon chain length of C-? 2 or greater, particularly carbon chain lengths of C-14/15 or even up to C? 6-18- In preferred embodiments of the detergent compositions of the invention comprising anionic surfactant, there will be a significant excess of anionic surfactants, preferably a weiratio of anionic to cationic surfactant of 50: 1 to 2: 1, preferably 2: 1: However, the benefits of the invention are also achieved when the ratio between cationic surfactant and anionic surfactant is substantially stoichiometric, for example from 3: 2 to 4: 3. In a preferred embodiment of the invention, the essential cationic surfactant of formula I is intimately mixed with one or more anionic surfactants before the addition of the other components of the detergent composition.

Carboxylate Anionic Surfactant Suitable carboxylate anionic surfactants include alkylethoxycarboxylates, alkylpolyethoxy polycarboxylates and soaps ("alkylcarboxyls"), especially certain secondary soaps as described herein. Suitable alkyleoxycarboxylates include those with the formula RO (CH2CH20) xCH2C00-M +, wherein R is an alkyl group of CQ to C-18. x varies from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material in which x is 0 is less than 20%, and M is a cation. Suitable alkylpolyethoxy polycarboxylate surfactants include those having the formula RO- (CHR <] -CHR2-O) -R3 wherein R is an alkyl group from CQ to C ^, x is from 1 to 25, R- | and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 to and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are the water soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, -propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Alkali metal sarcosinate surfactant agent Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R1) CH2COOM, wherein R is a linear or branched C5-C17 alkyl or alkenyl group, R1 is a group C1-C4 alkyl and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Non-ionic alkoxylated surfactant Essentially any alkoxylated nonionic surfactant is suitable herein. Preferred are ethoxylated and propoxylated nonionic surfactants. Linear or branched alkoxylated groups are suitable. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, ethoxylated / propoxylated nonionic fatty alcohols, ethoxylated / propoxylated non-ionic condensates with propylene glycol and the non-ionic ethoxylated condensation products with adducts of propylene oxide / ethylenediamine.

Nonionic surfactant of alkoxylated alcohol The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2c? NR1Z, wherein: R ^ is H, C1-C4 hydrocarbyl, 2-hydroxyethyl , 2-hydroxypropyl, ethoxy, propoxy, or a mixture thereof, preferably C1-C4 alkyl, most preferably C- alkyl; or C2, more preferably C- alkyl; (ie, methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C5-C19 alkyl or alkenyl, most preferably straight chain C9-C17 alkyl or alkenyl, more preferably CJ-J-CJ alkyl or alkenyl of straight chain or a mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably derive from a reducing sugar in a reductive amination reaction; most preferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant Suitable fatty acid amide surfactants include those having the formula: R6CON (R7) 2 wherein Rβ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R ^ is selected from the group consisting of hydrogen, C1-C4 alkyl, hydroxy C-1-C4, and - (C2H4?) xH, where x is on the scale of 1 to 3.

Alkylpolysaccharide Nonionic Surfactant The suitable alkylpolysaccharides which are used herein are described in the US patent. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, e.g., a polyglycoside, a hydrophilic group containing from 1.3 to 10. Units of taking out. Preferred alkyl polyglycosides have the formula R2? (CnH2nO) t (glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Amphoteric Surfactant Amphoteric surfactants suitable for use herein include the amine oxide surfactants and the alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) XN0 (R5) 2J wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing from 8 to 26 carbon atoms. carbon; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ^ is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C 10 -C 18 alkyldimethylamine oxide and acylamidoalkyldimethylamine oxide of C? o-C-18- A suitable example of an alkylamphodicarboxylic acid is Miranol (MR) C2M Conc., manufactured by Miranol, Inc., Dayton, New Jersey.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated into the detergent compositions herein. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are examples of zwitterionic surfactants that can be used herein. Suitable betaines are those compounds having the formula: R (R ') 2N + R2COO- where R is a hydrocarbyl group of Cg-C-is, each R1 is typically C1-C3 alkyl, and R2 is a hydrocarbyl group of C-j-C5. Preferred betaines are the C-12-C18 dimethylammonium hexanoate betaines and the acylamidopropane- (or ethane) dimethyl- (or diethyl) betaines of C < | rj-C-J8- Complex betaine surfactants are also suitable for use herein.

Additional Cationic Surfactants Preferably, the compositions of the invention are substantially free of quaternary ammonium compounds of the formula I, but wherein one or R ^, R2, R3 O R4 is an alkyl chain group greater than Cj -j . Preferably, the composition should contain less than 1%, preferably less than 0.1% by weight or even less than 0.05% and more preferably less than 0.01% by weight of compounds of the formula I having a linear (or even branched) alkyl group that has 12 or more carbon atoms. Another suitable group of cationic surfactants that can be used in the detergent compositions of the invention are the cationic ester surfactants. The cationic ester surfactant is a compound having surfactant properties and comprising at least one ester link (i.e., -COO-) and at least one cationically charged group. Preferred cationic ester surfactants are water dispersible. Suitable cationic ester surfactants, including choline ester surfactants, have been described, for example, in US Patents. Nos. 422,8042, 4239660 and 4260529. In the preferred cationic ester surfactants, the ester linkage and the cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (ie, with a chain length of three atoms), preferably three to eight atoms, most preferably three to five atoms, more preferably three atoms. The atoms forming the chain of the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms, and any mixtures thereof, with the proviso that no nitrogen or oxygen atom in said chain connects only with the atoms of carbon in the chain. In this way, groups which have, for example, links -OO- (ie, peroxide), -NN- and -N-0- are excluded, but include separating groups that have, for example, -CH2 bonds -O-CH2- and -CH2-NH-CH2. In a preferred aspect, the chain of the spacer group only comprises carbon atoms, most preferably the chain is a hydrocarbyl chain.

Fabric Softening Compounds Compounds having fabric softening properties are preferred additional detergent components. Suitable fabric softening compounds include cationic fabric softening materials and nonionic fabric softening materials. Suitable materials include substantially quaternary ammonium compounds substantially insoluble in water as described in EP 89200545.5 and EP 239910; amine materials; amphoteric fabric conditioning materials as described in EP 89200545.5, clays, polysiloxanes as described in EP-A-150867 (Procter &Gamble) Co.); and nonionic cellulose ethers as described in EP-A-213730 (Unilever).

Alkalinity In the detergent compositions of the present invention, an alkalinity system is preferably present to achieve optimum performance of the cationic ester surfactant. The alkalinity system comprises components capable of providing alkalinity species in the solution. For species of alkalinity we try to say in the present: carbonate, bicarbonate, hydroxide, the different anions of silicate, percarbonate, perborates, perfosfatos, persulfato and persilicato. Said alkalinity species may be formed, for example, when the alkali salts selected from carbonate, bicarbonate, hydroxide or alkali metal or alkaline earth metal silicate salts, including crystalline layered silicate and mixtures thereof are dissolved in water. Examples of carbonates are the alkaline earth metal and alkali metal carbonates, including sodium carbonate and sesqu carbonate and any mixture thereof with ultra fine calcium carbonate such as those described in German Patent Application No. 2,321,001. published November 15, 1973. Suitable silicates include soluble sodium silicates with a ratio of Si? 2: Na2? from 1.0 to 2.8, preferring ratios of from 1.6 to 2.0, and preferring more a ratio of 2.0. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with a ratio of Si? 2: Na2? 2.0 is the most preferred silicate.

Preferred crystalline layered silicates for use herein have the general formula: NaMSix? 2? + I VH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are described in EP-A-0164514, and methods for their preparation are described in DE-A-3417649 and DE-A-3742043. Here, x in the above general formula preferably has the value of 2, 3 or 4, and is preferably 2. The most preferred material is d-Na2Si2? S, available from Hoechst AG as NaSKS-6.

Water-soluble detergent-enhancing compound The detergent compositions according to the present invention preferably contain a water-soluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight , more preferably from 20% to 60% by weight of the composition. Water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxylic radicals separated from one another by no more of two carbon atoms, borates, phosphates and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxyl group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxyl groups include the water soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinylcarboxylates. Polycarboxylates containing three carboxyl groups include, in particular, citrates, aconitrates and water-soluble citraconates, as well as the succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1, 379,241, the lactoxysuccinates described in British Patent No. 1, 389,732 and the aminosuccinates described in Dutch application 7205873 and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanedicarboxylates described in British Patent No. 1, 387,447. The polycarboxylates containing four carboxyl groups include the oxydisuccinates described in British Patent No. 1, 261, 829, 1, 1, 2,2-ethane-tetracarboxylates, 1,1, 3,3-propane tetracarboxylates and the 1, 1, 2,3-propanotetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patents Nos. 1, 398,421 and 1, 398,422 and the patent of E.U.A. No. 3,936,448 and the sulfonated pyrolysed citrates described in British Patent No. 1, 439,000. Preferred polycarboxylates are hydrocarboxylates containing up to three carboxyl groups per molecule, most particularly citrates. The originating acids of monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g., mixtures of citric acid or citrate / citric acid are also contemplated as useful builders components. Borate builders, as well as builders that contain borate-forming materials that can produce borate under detergent storage or wash conditions, are water soluble builders useful herein. Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphate, potassium and sodium orthophosphate, and sodium polymetaphosphate, in which degree of polymerization varies from about 6 to 21, and salts of phytic acid.

Partially soluble or insoluble detergency meavator compound The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight , most preferably from 20% to 60% by weight of the composition. Examples of detergents largely soluble in water include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Naz [(Al? 2) z (Si? 2) and] -xH2? where z and y are integers of at least 6; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, most preferably from 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline, containing from 10% to 28%. %, most preferably from 18% to 22% water in bound form. The aluminosilicate zeolites may be materials of natural origin, but preferably are derived synthetically. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof. Zeolite A has the formula Nai 2 [(AI02) 12 (Si02) i 2. xH2? wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(Al? 2) 86 (SiO2) l06--76 H2O.

Another aluminosilicate zeolite that is preferred is the zeolite MAP builder. The zeolite MAP can be present at a level of 1% to 80%, most preferably 15% to 40% by weight of the compositions. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicone to aluminum ratio of not more than 1.33, preferably in the range of 0.9 to 1.33 and most preferably in the range of 0.9 to 1.2. Of particular interest is zeolite MAP which has a silicon to aluminum ratio of no more than 1.15, most particularly not more than 1.07. In a preferred aspect, the zeolite builder MAP has a particle size, expressed as a dso value of 1.0 to 10.0 microns, most preferably 2.0 to 7.0 microns, more preferably 2.5 to 5.0 microns. The value d ^ Q indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size can be determined in particular by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods to establish the dso values are described in EP 384070A.

Heavy metal ion sequestrant The detergent compositions or components thereof according to the present invention preferably contain a heavy metal ion sequestrant as an optional component. By heavy metal ion sequestrant is meant here components that act to sequester (chelate) heavy metal ions. These components may also have the ability to chelate calcium and magnesium, but preferably show selectivity for binding to heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level of 0.005% to 20%, preferably 0.1% to 10%, most preferably 0.25% to 7.5% and more preferably 0.5% to 5% by weight of the compositions . Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethan-1-hydroxydiphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminpenta (methylenephosphonate), ethylenediamtrn- (methylenephosphonate), hexamethylenediaminetetra (methylene phosphonate) and hydroxyethylene-1,1-diphosphonate. Another heavy metal ion sequestrant suitable for use herein includes nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminpentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinic acid or any salt thereof. Especially preferred is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. Other heavy metal ion sequestrants suitable for use herein are the iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl iminodiacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid-N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The sequestrants of β-alanin-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid described in EP-A-509,382 are also suitable. EP-A-476,257 describes suitable amine-based sequestrants, EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 discloses a suitable alkyliminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutan-1, 2,4-tricarboxylic acid. Glycinamide-N-N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Organic Peroxyacid Bleaching System A preferred feature of the detergent compositions or component thereof according to the invention is an organic peroxyacid bleaching system. In a preferred embodiment, the bleach system contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In a preferred and alternative embodiment, a preformed organic peroxyacid is incorporated directly into the composition. Also contemplated are compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Inorganic Perhydrate Blangogens The inorganic salts of perhydrate are a preferred source of hydrogen peroxide. These salts are normally incorporated in the alkali metal form, preferably sodium salt at a level of 1% to 40% by weight, most preferably from 2% to 30% by weight and more preferably from 5% to 25% by weight of the salts. compositions Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional protection. However, for certain perhydrate salts, the preferred embodiments of said granulated compositions use a coated form of the material, which provides better storage stability for the perhydrate salt in the granulated product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils or fatty soaps. Sodium perborate is a preferred perhydrate salt and may be in the form of the monohydrate of the nominal formula NaB 2 H 2 o 2 or the tetrahydrate Na B 2 H 2 2.3 2.3 H 2. The alkali metal percarbonates, particularly sodium percarbonate, are the perhydrates that are preferred herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C? 3.3H2? 2 and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. The peroxyacid bleach precursors can generally be represented as: O I I X - C - L wherein L is a leaving group and X is essentially any functionality, such that perhydrolysis, the structure of the produced peroxyacid is: O I I X-C-OOH The peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, most preferably from 1% to 15% by weight, more preferably from 1.5% to 10% by weight of the detergent compositions. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and adidas derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Outgoing groups The leaving group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (eg, a wash cycle). However, if L is very reactive, it will be difficult to stabilize this activator for use in a bleaching composition. The preferred L groups are selected from the group consisting of: and mixtures thereof, wherein R ^ is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.

Any of R1, R3 and R4 may be substituted essentially with any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups. The preferred solubilizing groups are -S? 3_M +, -C? 2"M +, -SO4" M +, -N + (R3) 4X "and O <- N (R3) 3, and most preferably -S? 3" M + and -C? 2_M +, in wherein R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with more sodium and potassium being preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkylpercarboxylic acid bleach precursors The alkylpercarboxylic acid bleach precursors form percarboxylic acids by perhydrolysis. Preferred precursors of this type provide peracetic acid by perhydrolysis. Preferred alkylcarboxylic acid precursor compounds of the metric type include the NNN'lN'l-tetraacetylated alkylenediamines in which the alkylene group contains 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 to 2 carbon atoms. and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS), sodium nonailoxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Precursors of aliphenylperoxy substituted with amide The amide substituted alkylperoxy acid precursor compounds are suitable herein, including those having the following general formulas: R1-C- N-R2"C- L R1 -N- C- R2" C- L I I I I I I I I I I O R5? Rd O O wherein R1 is an alkyl group with 1 to 14 carbon atoms, R2 is a alkylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl group containing 1 to 10 carbon atoms, and L can be essentially any leaving group. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid by perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzenesulfonates and the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, and those of the metric type including N-benzoylsuccinimide, tetrabenzoylethylenediamine and the N-benzoyl substituted ureas. Suitable midazole perbenzoic acid precursors include N-benzoyimidazole and N-benzoylbenzimidazole. Other perbenzoic acid precursors containing a useful N-acyl group include N-benzoylpyrrolidone, dibenzoyltaurine and benzoyl pyrglutamic acid.

Cationic Peroxyacid Precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids by perhydrolysis. Typically, cationic peroxyacid precursors are formed by replacing the peroxyacid portion of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid precursors are typically present in solid detergent compositions as a salt with a suitable anion, such as a halide ion. The peroxyacid precursor compound which will be cationically substituted may be a perbenzoic acid precursor compound or a substituted derivative thereof as described hereinabove.

Alternatively, the peroxyacid precursor compound may be an alkylpercarboxylic acid precursor compound or an amide substituted alkylperoxy acid precursor as described hereinafter. Cationic peroxyacid precursors are described in the U.S. Patents. Nos. 4,904,406, 4,751, 015; 4,988,451; 4,397,757; 5,269,962; ,127,852; 5,093,022; 5,106,528; U.K. 1, 382.594; EP 475,512, 458,396 and 284.292; and in JP 87-318,332. Examples of preferred cationic peroxyacid precursors are described in United Kingdom patent application No. 9407944.9 and in the patent applications of E.U.A. Nos. 08/298903, 08/298650, 08/298904 and 08/298906 Suitable cationic peroxyacid precursors include any of the substituted ammonium or alkylammonium alkyl- or benzoyloxybenzenesulfonates, the N-acylated caprolactams and the benzoylperoxides of monobenzoyltetraacetylglucose. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkylammonium methylenebenzoylcaprolactams and trialkylammonium methylenealkylcaprolactams.

Benzoxazine organic peroxyacid precursors Benzoxazine precursor compounds such as those described for example in EP-A-332,294 and EP-A-482,807 are also suitable, particularly those having the formula: wherein R-j is H, alkyl, alkaryl, aryl or arylaikyl.

Preformed Organic Peroxyacid The organic peroxyacid bleach system may contain, in addition to, or as an alternative to, a precursor organic peroxyacid bleach compound, a preformed organic peroxyacid, typically at a level of 1% to 15% by weight, most preferably from 1% to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulas: R1-C- N-R2 -C- OOH R1"N- C- R2" C-OOH O R5 O Rd o O wherein R ^ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl group or alkaryl containing from 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386. Other organic peroxyacids include the diacyl- and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecane-dioic acid. Also suitable here are mono- and diperazelaic acid, mono- and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid.

Bleach Catalyst The compositions optionally contain a bleach catalyst containing a transition metal. A suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no catalytic bleaching activity , such as zinc or aluminum cations and a sequestrant having defined stability constants for the auxiliary metal and catalytic cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra- (methylene phosphonic acid) and the water soluble salts thereof. Said catalysts are described in the patent of E.U.A. No. 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in the U.S.A. No. 5,246,621 and in the patent of E.U.A. No. 5,244,594. Preferred examples of these catalysts include MnlV2 (u-O) 3 (1, 4,7-trimetiI-1, 4,7-triazacyclononane) 2- (PF6) 2. Mn '|| 2 (u- 0) 1 (u-OAc) 2 (1, 4,7-trimetiM, 4,7-triazacyclononane) 2- (Cl? 4) 2, Mn'V4 (u- O) ß (1, 4,7-triazacyclononane) 4- (Cl? 4) 2, Mn '|| MnIV4 (u-0)? (u-OAc) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (CI? 4) 3 and mixtures thereof. Others are described in the publication of the European patent application No. 549, 272. Other ligands suitable for use herein include 1, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1, 4,7-triazacyclononane, 2-methyl-1, 4,7-triazacyclononane, 1 , 2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof. For examples of suitable bleach catalysts see the patent of E.U.A. No. 4,246,612 and in the patent of E.U.A. No. 5,227,084. See also the patent of E.U.A. No. 5,194,416, which teaches mononuclear manganese (IV) complexes such as Mn (1, 4,7-trimetiM, 4,7-triazacyclononane) (OCH 3) 3 (PF 6). Yet another type of bleach catalyst such as that described in the U.S.A. No. 5,114,606 is a water soluble complex of manganese (III) and / or (IV) with a ligand that is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4Mn '"(u-O) 2MnlVN4) + and [B and p2Mnl "(uO) 2Mnl bipy2] - (Cl? 4) 3. Suitable and additional bleach catalysts are described, for example, in European Patent Application No. 408,131 (cobalt complex catalysts), applications European Patent Publication Nos. 384,503 and 306,089 (metalloporphyrin catalysts), US Patent 4,728,455 (manganese / multidentate ligand catalyst), US Patent 4,711,748 and European Patent Application Publication No. 224,952 (Manganese Catalyst Absorbed on aluminosilicate), U.S. Patent 4,601, 845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. Patent 4,626,373 (manganese / ligand catalyst), U.S. Patent 4,119,557 (ferric complex catalyst), German patent description 2,054,019 (cobalt-chelating catalyst), Canadian 866,191 (salts containing transition metals), US 4,430,243 (chelating agents with manganese cations and non-catalytic metal cations) ico) and of E.U.A. 4,728,455 (manganese gluconate catalysts).

Additional Enzymes The compositions of the present invention may comprise one or more additional enzymes. Additional preferred enzyme materials include commercially available enzymes. Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, glucoamylases, amylases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, β-glucanases , arabinosidases, hyalurodinase, chondroitinase, laccase or mixtures thereof. A preferred combination of additional enzymes is a cleaning composition having a mixture of conventional applicable enzymes such as protease, amylase, cutinase and / or cellulase, in conjunction with one or more plant cell wall degrading enzymes. Suitable enzymes are described in the US patents. Nos. 3,519,570 and 3,533,139. Suitable proteases are subtilisins, which are obtained from particular strains of B. subtilis and ß. licheniformis (subtilisin BPN and BPN '). A suitable protease is obtained from a strain of Bacillus, which has maximum activity on the whole pH scale of 8 to 12, developed and sold as WAIT ^ of Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784 of Novo Other suitable proteases include ALCALASER, DURAZYMR and SAVINASER de Novo and MAXATASER, MAXACALR, PROPERASER and MAXAPEMR (protein designed by genetic engineering) of Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases such as those described in European Patent Application Serial No. 87 303761.8, filed on April 28, 1987 (in particular pages 17, 24 and 98), and which are incorporated herein by reference. dominates here "Protease B" and in the European patent application 199,404, Venegas, published on October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme, referred to herein as "protease A". More preferred is what is referred to herein as "protease C", which is a variant of a Bacillus alkaline serine protease, in which lysine replaces arginine in position 27, tyrosine replaces valine in position 104 , serine replaces asparagine at position 123, and alanine replaces threonine at position 274. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published May 16, 1991 Also included are the genetically modified variants, particularly of protease C. A preferred protease, referred to as "protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a carbonyl hydrolase precursor replacing a different amino acid from a plurality of amino acid residues at a position in said equivalent carbonyl hydrolase at position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274, according to the numbering of the subtilisin of Bacillus amyloliquefaciens, as described in WO95 / 10591 and in the patent application of C. Ghosh, et al., "Bleachin Compositions Comprising Protease Enzymes", which has serial number from the USA No. 08 / 322,677, filed October 13, 1994. Also suitable for the present invention are the proteases described in patent applications EP 251 446 and WO 91/106637 and the BLAPR protease, described in WO 91/02792 and its variants described in WO 95/23221 See also a high pH protease from Bacillus sp. NCIMB 40338 which is described in WO 93/18140 A for Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A for Novo. When desired, a protease having reduced adsorption and increased hydrolysis is available, as described in WO 95/07791 for Procter & amp; amp;; Gamble. A recombinant trypsin-like protease for detergents, which is suitable for the present invention, is described in WO 94/25583 to Novo. In EP 516 200 to Unilever, other suitable proteases are described. In the detergent compositions of the present invention a proteolytic enzyme or a mixture thereof may be incorporated, usually at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, preferably from 0.005% to 0.1 % pure enzyme by weight of the composition. In the detergent compositions of the present invention, the enzyme component (policy is generally present at levels of 0.00005% to 2% active enzyme by weight of the detergent composition, preferably from 0.001% to 1%, preferably from 0.002% to 0.05% by weight of active enzyme in the detergent composition.

Suitable lipolytic enzymes for use in the present invention include those produced by microorganisms from the group of Pseudomonas, such as Pseudomonas stutzeri ATCC 19,154, as described in British Patent 1, 372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody produced by the Pseudomonas microorganism Hisorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co.

Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, Chromobacter viscosum lipases, e.g., Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., E.U.A. and Disoynth Co., The Netherlands and the lipases of Pseudomonas gladioli. Particularly suitable lipases are lipases such as Ml Lipase® and Lipomax® (Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever. Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special type of lipase, namely lipases that do not require interfering activation. The addition of cutinases to detergent compositions has been described in e.g., WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever). The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341, 947) is a lipase which is preferred to be used in the present invention. Another lipase that is preferred to be used in the present invention is the lipolytic enzyme variant D96L of the native lipase derived from Humicola lanuginosa. Most preferably, strain DSM 4106 from Humicola lanuginosa is used. By variant of the lipolytic enzyme D96L is meant the lipase variant as described in the patent application WO 92/05249, in which the native lipase of Humicola lanuginosa has the residue of aspartic acid (D) in position 96 changed to leucine (L). According to this nomenclature, said substitution of aspartic acid to leucine in position 96 is shown as: D96L. To determine the activity of the D96L enzyme, the normal LU test can be used (analytical method, internal Novo Nordisk AF 95/6-GB 1991.02.07). A substrate for D96L was prepared by emulsifying glycerin tributyrate (Merck) and using gum arabic as an emulsifier. The activity of the lipase is tested at pH 7 using the statistical pH method. • The detergent compositions of the invention may also contain one, or a mixture of more than one amylase (and / or β) enzyme. WO94 / 02597, Novo Nordisk A / S published on February 3, 1994, describes cleaning compositions incorporating mutant amylases. See also WO95 / 10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in cleaning compositions include both α and β amylases. The α-amylases are known in the art and include those described in the U.S. patent. No. 5,003,257; EP 252,666; WO / 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and in the description of British Patent No. 1, 296,839 (Novo). Other suitable amylases are the amylases of improved stability described in W094 / 18314, published on August 18, 1994 and WO96 / 05295, Genencor, published on February 22, 1996, as well as the amylase variants having a further modification in the Immediate parent available from Novo Nordisk A / S, described in WO 95/10603, published April 25, 1995. Also suitable are the amylases described in EP 277 216, W095 / 26397 and WO96 / 23873 (all from Novo Nordisk). Examples of commercial a-amylases products are Purafect Ox AmR from Genencor and Termamyl®, Ban ^, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S, Denmark. WO95 / 26397 describes other suitable amylases: α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl at a temperature range of 25 ° C to 55 ° C and a pH value in scale from 8 to 10, as measured by the Phadebas® α-amylase activity test. The variants of the above enzymes, described in WO96 / 23873 (Novo Nordisk), are suitable. Other preferred amylolytic enzymes with improved properties with respect to the level of activity and the ination of thermostability, as well as a higher activity level are described in WO95 / 35382. Amylolytic enzymes, if present, are generally incorporated in the detergent ositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, most preferably from 0.00024% to 0.048% pure enzyme by weight of the osition. The detergent ositions of the invention may also contain one or more cellulase enzymes. Suitable cellulases include both bacterial and fungal cellulases. Preferably, they will have an optimum pH of between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are described in the U.S. patent. 4,435,307, Barbesgoard et al., J61078384 and WO96 / 02653, which describe fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel species of Bacillus. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275; DE-OS-2,247,832 and W095 / 26398. Examples of said cellulases are the cellulases produced by a strain of Humicola insolens (Humicola grísea var, thermoidea), particularly the DSM 1800 strain of Humicola. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of approximately 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ~ 43kD endoglucanase derived from Humicola insolens, DSM 1800, which exhibits cellulase activity; an endoglucanase onent that is preferred has the amino acid sequence described in PCT patent application No. WO 91/17243. Cellulases which are also suitable are the EGEIII cellulases of Trichoderma longibrachiatum described in WO94 / 21801, Genencor, published on September 29, 1994. Particularly suitable cellulases are cellulases which have color care benefits. Examples of said cellulases are the cellulases described in the European patent application No. 91202879.2, filed on November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO91 / 17244 and WO91 / 21801. Other cellulases suitable for fabric care and / or cleaning properties are described in WO96 / 34092, WO96 / 17994 and WO95 / 24471. Peroxidase enzymes can also be incorporated into the detergent ositions of the invention. Peroxidases are used in ination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching in solution", that is, to avoid the transfer of dyes or pigments removed from substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidases, ligninase peroxidase and halogen peroxidases, such as chlorine and bromoperoxidases. Peroxidase-containing detergent ositions are described, for example, in International Patent Application WO 98/099813, WO89 / 09813 and European Patent Application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed on February 20, 1996. The laccase enzyme is also suitable. Preferred enhancers are substituted phenoxyzine and phenoxazine and 10-phenothiazine propionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenothiazinpropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and the substituted syringates (substituted C3-C5 alkylsalicylates) and phenols. Percarbonate or sodium perborate are the preferred sources of hydrogen peroxide. Said cellulases and / or peroxidases, if present, are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Said additional enzymes, when present, are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Additional enzymes can be added as separate individual ingredients (pellets, granules, stabilized liquids, etc. containing an enzyme) or as mixtures of two or more systems (eg, cogranulates).

Enzyme oxidation scavengers Other suitable detergent ingredients that may be added are the enzyme oxidation scavengers described in co-pending European patent application 92870018.6, filed on January 31, 1992.

Examples of said enzyme oxidation scavengers are the ethoxylated polyamines.

Enzyme materials A range of enzyme materials and means for their incorporation into synthetic detergent compositions are also described in WO 9307263 and WO 9307260 from Genencor International, WO 8908694 A from Novo, and US Pat. 3,553,139, January 5, 1971 by McCarty et al. Enzymes are also described in the U.S. patent. 4,101, 457, Place et al., July 18, 1978 and in the US patent. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in US Pat. 4,261, 868, Hora et al., April 14, 1981. The enzymes that will be used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in the US patent. 3,600,319, August 17, 1991, Gedge et al., EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in the U.S. patent. 3,519,570. A Bacillus, AC13 useful and which gives proteases, xylanases and cellulases, is described in WO 9401532 A de Novo.

Organic polymeric compound Organic polymeric compounds are preferred additional components of the detergent compositions or components thereof according to the invention, and are preferably present as components of any particulate components, where they can act to bind the particulate component together . By "organic polymeric compound" is meant herein essentially any polymeric organic compound that is not an oligoester or polyamine soil remover polymer, and that is commonly used as a dispersant and anti-redeposition agent and suspension of soils in detergent compositions , including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein. This organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions. Examples of organic polymeric compounds include organic homo- or copolymeric water-soluble polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms. Polymers of the latter type are described GB-A-1, 596,756. Examples of such salts are polyacrylates of MW 1000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of 2000 to 100,000, especially 40,000 to 80,000. Polymaleate or polymaleic acid polymers and salts thereof are also suitable examples. Polyamino compounds are useful herein, including those derived from aspartic acid such as those described in EP-A-305282, EP-A-305283 and EP-A-351629. Also suitable for incorporation into the compositions of the present invention are terpolymers containing selected monomeric units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 1,000 to 30,000. Preference from 3,000 to 10,000. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include essentially any charged and uncharged cellulose derivative such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Additional organic polymeric compounds and useful with polyethylene glycols, particularly those with a molecular weight of 1000-10000, very particularly 2000 to 8000 and more preferably around 4000.

Cationic removal / anti-redeposition compounds of dirt The detergent composition or components thereof according to the invention can comprise water-soluble cationic ethoxylated amine compounds with removal / anti-redeposition properties of dirt / clay soils. These cationic compounds are described in more detail in EP-B-111965, US 4659802 and US 4664848. Ethoxylated cationic monoamines, diamines or cationic triamines are particularly preferred among these cationic compounds. Ethoxylated cationic monoamines, diamines or triamines of the formula are especially preferred: wherein X is a nonionic group selected from the group consisting of H, C-1-C4 alkyl or hydroxyalkyl ester or alkyl groups, and mixtures thereof, a is 0 to 20, preferably 0 to 4 (v .gr., ethylene, propylene, hexamethylene), b is 2, 1 or 0; for cationic monoamines (b = 0), n is preferably at least 16, with a typical scale of 20 to 35; for cationic diamines or triamines, n is preferably at least about 12, with a typical scale of about 12 to about 42.

These compounds, when present in the composition, are generally present in an amount of 0.01 to 30% by weight, preferably 0.05 to 10% by weight.

Foam suppression system The detergent compositions of the invention, when formulated for use in machine wash compositions, preferably comprise a foam suppression system present at a level of 0. 01% to 15%, preferably from 0.05% to 10% and most preferably from 0.1% to 5% by weight of the composition. The foam suppression systems suitable for use herein can comprise essentially any known antifoam compound, including, for example, silicone anti-foaming compounds and 2-alkylalcanol antifoaming compounds. By "antifoaming compound" is meant herein any compound or mixtures of compounds which act to reduce the foaming produced by a solution of a detergent composition, particularly in the presence of the agitation of that solution. Particularly preferred defoaming compounds for use herein are the silicone anti-foaming compounds defined herein as any defoaming compound that includes a silicone component. Said silicone anti-foaming compounds also typically contain a silica component. The term "silicone", as used herein and generally in the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and a hydrocarbyl group of various types. Preferred antifoaming silicone compounds are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable defoaming compounds include the monocarboxylic fatty acids and the soluble salts thereof. These materials are described in the U.S. patent. No. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof for use as foam suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as the sodium, potassium and lithium salts, and the ammonium and alkanolammonium salts. Other suitable defoaming compounds include, for example, high molecular weight fatty esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C-18-C40 ketones (e.g., stearone) ), N-alkylated amino triazines such as tri- or hexa-alkylmelamines or di- to tetra-alkyldiaminclortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and the di-alkali metal monostearyl phosphates (e.g., sodium, potassium, lithium) and phosphate esters. A preferred foam suppressor system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination: (i) polydimethylsiloxane, at a level of 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound; wherein said silica / silicone antifoam compound is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight; (b) a dispersing compound, most preferably comprising a silicone glycol copolymer with a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of from 1: 0.9 to 1: 1.1, at a level of 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred glycol silicone hardener copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544; (c) an inert carrier fluid composition, most preferably comprising an ethoxylated C-je-C-is alcohol with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5% to 80%, preferably 10% to 70% by weight; A highly preferred particulate foam suppression system is disclosed in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point on the scale of 50 ° C to 85 ° C, wherein The organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate foam suppressor systems in which the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms or a mixture thereof , with a melting point of 45 ° C to 80 ° C.

Polymeric Dye Transfer Inhibitory Agents The detergent compositions herein can also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents. The polymeric dye transfer inhibiting agents are preferably selected from copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers can be entangled polymers. a) Polyamine N-oxide polymers The polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: P (I) Ax I R where P is a polymerizable unit, and O R 1 R 1 O O R 1 I I I I I I I A is -C-N-, -N- C-, CO, C, -O-, -S-, -N-; x is 0 or 1; R1 is H or straight or branched alkyl of or can form a heterocyclic group with R; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups, or any combination thereof, to which the nitrogen of the N-O group may be attached, or wherein the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following general structures: 0 O 1 I (R x - N - (R2) and o = N- (R?) X (R3) z wherein R1, R2 and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, xy / oyy / oz is 0 or 1, and wherein the nitrogen of the NO group may be attached, or wherein the nitrogen of the group is NOT part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be attached to the polymeric backbone, or a combination of both.

Suitable polyamine N-oxides, wherein the N-O group forms part of the polymerizable unit, comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the NO group is part of the R group. The preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine , pyrrole, midazole, pyrrolidine, piperazine, quinoline, acridine and derivatives thereof. Other suitable polyamine N-oxides are the polyamine oxides to which the N-O group is attached to the polymerizable unit. A preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group wherein the nitrogen of the functional group is NOT part of said group R Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, midazole and derivatives thereof. The polyamine N-oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, as long as the material has the desired water solubility and the desired dye suspension power. Typically, the average molecular weight is within the range of 500 to 1,000,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole The polymers of N-vinylimidazole-N-vinylpyrrolidone used herein have an average molecular weight scale of 5,000 to 50,000, or 5,000 to 50,000. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2. c) Polyvinylpyrrolidone The detergent compositions herein can also use polyvinylpyrrolidone ("PVP"), which has an average molecular weight of from about 2,500 to about 400,000. Suitable polyvinyl pyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the trademarks PVP K-15 (molecular weight of 10,000 with viscosity), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinyl pyrrolidones which are commercially available from BASF Corporation, include Sokalan HP 165 and Sokalan HP 12. d) Polyvinyloxazolidone The detergent compositions of the present invention can also use polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000. e) Polyvinylimidazole The detergent compositions of the present invention can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinyl imidazoles have an average molecular weight of 2,500 to 400,000.

Optical Brightener The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful herein are those that have the structural formula: where R- | it is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the previous formula, R- | is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4 'acid, bis [(4-anilino-6- (N-2-bis-hydroxyethyl)) -s-triazin-2-yl) amino] -2,2'-stilbene-disulfonate and disodium salt. This particular brightener species is commercially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbene-disulfonic acid. This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX from Ciba-Geigy Corporation. When in the above formula Ri is anilino, R2 is morphiino, and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-aniolin-6-morphino-s-triazin- 2-yl) amino] 2,2'-stilbene-disulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX from Ciba-Geigy Corporation.

POLYMERIC POLISH REMOVAL AGENT The known polymeric soil removal agents, hereinafter "SRA", can optionally be used in the present detergent compositions. If used, the SRA's will generally comprise from about 0.01% to 10.0%, typically from about 0.1% to 5%, preferably from about 0.2% to 3.0% by weight, of the compositions. Preferred SRA's typically have hydrophilic segments to hydrophilicize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on and remain adhered to hydrophobic fibers until the washing and rinsing cycles are completed, thus serving as a anchoring for hydrophilic segments. This can make it possible to more easily cleanse the spots that occur after treatment with the SRA in subsequent washes. Preferred SRAs include oligomeric terephthalate esters, typically prepared by methods that include at least one transesterification / oligomerization, commonly with a metal catalyst such as a titanium (IV) alkoxide. Said esters can be manufactured using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely intertwined overall structure. Suitable SRA's include a sulphonated product of a substantially linear ester oligomer formed from an oligomeric ester backbone of terephthaloyl and oxyalkylenoxy repeat units and sulfonated end portions derived from allyl covalently attached to the backbone, for example, as described in the US Pat. USA 4,968,451, November 6, 1990 by J. J. Scheibel and E.P. Gosselink. Said ester oligomers can be prepared: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two step transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the polyesters of 1, 2-propylene / polyoxyethylene terephthalate of non-ionic blocked ends of the U.S. patent. No. 4,711, 730, of December 8, 1987 to Gosselink and others, for example those produced by the transesterification / oligomerization of methyl ether of polyethylene glycol, DMT, PG and polyethylene glycol ("PEG"). Other examples of SRA's include: the oligomeric esters of anionic blocked ends partially and completely of the U.S. patent. No. 4,721, 580, from January 26, 1988 to Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctansulfonate; the non-ionic blocked block polyester oligomeric compounds of the U.S.A. 4,702,857, from October 27, 1987 to Gosselink, for example produced from DMT, PEG and EG and / or PG (Me) -blocked methyl or a combination of DMT, EG and / or PG, PEG Me-blocked and Na-dimethyl-5-sulfoisophthalate; and the blocked terephthalate esters of the anionic ends, especially of sulfoaroyl of the U.S. patent. No. 4,877,896 of October 31, 1989 to Maldonado Gosselink and others, the latter being a typical SRA's useful in both fabric conditioning and laundry products with one example being an ester composition made from the monosodium salt of the acid m- sulfobenzoic, PG and DMT, optionally but preferably further comprising added PG, e.g., PEG 3400. SRA's also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see the EU patent No. 3,959,230 to Hays of May 25, 1976 and the US patent. No. 3,893,929 to Basadur, July 8, 1975, cellulose derivatives such as the cellulosic hydroxyether polymers available as METHOCEL from Dow; the C-1-C4 alkyl celluloses and C4 hydroxyalkylcells of the U.S. patent. No. 4,000,093, from December 28, 1976 to Nicol, et al., And methyl cellulosic esters having an average degree of substitution (methyl) per anhydroglucose unit of about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoises measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the commercial brands of the methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRA's include: (I) non-ionic terephthalates using diisocyanate coupling agents to link the polymeric ester structures, see E.U. 4,201, 824, Violland et al. And E.U. 4,240,918 Lagasse et al., And (II) SRA's with carboxylate end groups made by adding trimethyl anhydride to known SRA's to convert terminal hydroxyl groups to trimethylate esters. With the proper selection of the catalyst, trimethyl anhydride forms bonds to the polymer terminals through a carboxylic acid ester isolated from the trimethyl anhydride instead of opening the anhydride linkage. Either non-ionic or anionic SRAs can be used as starting materials, as long as they have hydroxyl end groups that can be esterified, see E.U. No. 4,525,524 Tung and others. Other classes include (III) non-anionic terephthalate-based SRAs of the urethane-linked variety, see E.U. 4,201, 824, Violland et al .;Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colors and filler salts, with a preferred filler salt being sodium sulfate.

Detergent formulation with an almost neutral wash pH Although the detergent compositions of the present invention are operative within a wide range of wash pHs (e.g., from about 5 to about 12), they are particularly suitable when formulated to provide an almost neutral wash pH, ie, an initial pH of from about 7.0 to about 10.5 at a concentration of about 0.1 to about 2% by weight in water at 20 ° C. Formulations with an almost neutral wash pH are better for enzyme stability and to prevent stains from depositing. In such formulations, the wash pH is preferably from about 7.0 to about 10.5, most preferably from about 8.0 to about 10.5, more preferably from 8.0 to 9.0. Detergent formulations with an almost neutral wash pH are described in European patent application 83.200688.6, filed on May 16, 1983, J.H.M. Wertz and P.C.E Goffinet. Highly preferred compositions of this type also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, pH regulating agents. , phase regulators, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, foam regulators, opacifiers, antioxidants, bactericides, dyes, perfumes and brighteners, such as those described in the US patent 4,285,841 to Barrat et al., Issued August 25, 1981 (incorporated herein by reference).

Form of the Compositions The compositions according to the invention can have a variety of physical forms including the granulated forms, in tablets, flakes, bars, sticks and liquids. The liquids can be aqueous or non-aqueous and can be in the form of a gel. The compositions may be pretreatment compositions or conventional laundry detergents. The compositions are particularly so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a delivery device placed in the tub of the washing machine with the load of laundry. Said granular detergent compositions or components thereof according to the present invention can be made by a variety of methods, including dry blending, spray drying, extrusion, agglomeration and granulation. The quaternized surfactant can be added to the other detergent components by mixing, agglomeration (preferably combined with a carrier material) or as a spray-dried component. The compositions according to the present invention can also be used in or in combination with bleaching additive compositions, for example comprising chlorine bleach. In an aspect of the invention, the average particle size of the components of the granulated compositions according to the invention should preferably be such that no more than 15% of the particles are more than 1.8 mm in diameter and not more than 15% of the particles are less than 0.25 mm in diameter. Preferably, the average particle size is such that 10% to 50% of the particles have a particle size of 0.2 mm to 0.7 mm in diameter.

The term "average particle size" as defined herein is calculated by sieving a sample of the composition in a number of fractions (typically 5 fractions) in a series of sieves, preferably Tyler sieves. The fractions of weight thus obtained are plotted against the opening size of the sieves. The average particle size is considered the size of the opening through which 50% by weight of the sample would pass. In a further aspect of the invention, at least 80%, preferably at least 90% by weight of the composition comprises particles with an average particle size of at least 0.8 mm, most preferably at least 1.0 mm and more preferably 1.0, or 1.5 to 2.5 mm, More preferably at least 95% of the particles will have said average particle size. Said particles are preferably prepared by an extrusion process. The overall density of the granular detergent compositions according to the present invention is typically an overall density of at least 400, preferably 600 g / liter, most preferably from 650 g / liter to 1200 g / liter. The overall density is measured by means of a simple funnel-cup device consisting of a conical funnel rigidly molded on a base and provided with a butterfly valve at its lower end to allow the contents of the funnel to be emptied into a cylindrical cup aligned axially below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm in its respective upper and lower extremities. It is mounted in such a way that the lower extremity is 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml. To carry out a measurement, the funnel is filled with manually poured dust, the butterfly valve is opened and the powder is allowed to overfill the cup. The full cup is removed from the frame and the excess powder is removed from the cup by passing a straight edge implement, eg, a knife, through its upper edge. The full cup is then weighed and the value obtained for the weight of the powder is doubled to provide a global density in g / liter. Equal measurements are made as required. The compacted solids can be manufactured using any suitable compaction process, such as rattling, agglomeration or extrusion, preferably tableting. Preferably, the tablets that will be used in dishwashing procedures are manufactured using a normal rotary clack press and using compression forces of 5 to 13 KN / cm2, very preferably from 5 to 11 KN / cm2 so that the compacted solid has a minimum hardness of 176N to 275N, preferably 195N to 245N, measured by a C100 hardness test as provided by I. Holland instruments. This method can be used to prepare homogeneous or stratified tablets of any size or shape. Preferably, the tablets are symmetrical to ensure uniform dissolution of the tablet in the wash solution.

Laundry Washing Method The laundry washing methods of the present invention typically comprise treating the laundry with an aqueous washing solution in a washing machine having dissolved or supplied therein an effective amount of a laundry detergent composition in accordance with the present invention. with the invention For an effective amount of the detergent composition it is tried to say from 10g to 300g of product dissolved or dispersed in a washing solution of a volume of 5 to 65 liters, which are typical doses of product and in volumes of washing solution commonly used in conventional laundry washing methods. The dosage depends on the particular conditions such as water hardness and degree of soiling of the laundry. The detergent composition of the invention can be brought into contact with the fabric to be treated in a washing step or in a rinsing step.

The detergent composition can be supplied, for example, from the assortment box of a washing machine or it can be put in contact with the fabric to be treated in the machine. In one aspect of use, a delivery device is employed in the washing method. The delivery device is loaded with the detergent product and used to introduce the product directly into the drum of the washing machine before starting the washing cycle. Its volume capacity must be such that it is capable of containing sufficient detergent product that would normally be used in the washing method.

The delivery device containing the detergent product is placed inside the drum before the start of the washing cycle, before, simultaneously with or after the washing machine has been loaded with clothes. At the beginning of the washing cycle of the washing machine, water is introduced into the drum and it rotates periodically. The design of the delivery device must be such as to allow the dry detergent product to be contained but then allow this product to be released during the wash cycle in response to its agitation when the drum is turned and also as a result of its contact with the washing liquid. To allow the release of the detergent product during washing, the device may possess a number of openings through which the product can pass. Alternatively, the device may be made of a material that is liquid permeable but impermeable to the solid product, which will allow the dissolved product to be released. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing transient localized concentrations of the product in the drum of the washing machine at this stage of the wash cycle. The preferred delivery devices are reusable and are designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Especially preferred delivery devices for use with the composition of the invention have been described in the following patents: GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A- 0288346. An article by J. Bland, published in Manufacturing Chemist, November 19889, p. 41-46, also discloses especially preferred supply devices for use with granular laundry products, which are of a type commonly known as "granulette". Another preferred delivery device for use with the compositions of this invention is described in the PCT patent application NO. W094 / 11562. Essentially preferred delivery devices are described in European Patent Application Publication Nos. 0343069 and 0343070. This application describes a device comprising a flexible liner in the form of a pouch extending from a support ring defining an orifice, the orifice being adapted to admit sufficient product into the bag for a washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product and the solution then passes down through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent the exit of the moistened and undissolved product, this arrangement typically comprising radial walls extending from a protrusion in a spoke wheel configuration or similar structure, in which the walls They have a helical shape. Alternatively, the delivery device may be a flexible container, such as a bag or bag. The bag may be made of a fibrous structure coated with a waterproof protective material to retain the contents, such as that described in published European patent application No. 0018678. Alternatively, it may be formed of a synthetic polymeric material insoluble in water provided with an edge seal or seal designed to break in the aqueous medium as described in published European patent applications Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of frangible water closure comprises a soluble adhesive in water disposed along one edge of a sack, sealing it, formed of a water-impermeable polymeric film such as polyethylene and polypropylene. In general, the composition is brought into contact with clothing or fabric by washing at low temperatures of less than 40 ° C. The composition can even be contacted with the fabrics to be treated in cold water, for example at temperatures of less than 25 ° C, or even of less than 20 ° C.

Automatic dishwashing method Any suitable method is contemplated for the automatic washing of dishes or the cleaning of dirty cutlery, particularly dirty silverware. An automatic dishwashing method that is preferred comprises treating selected articles of earthenware, glassware, pots, silverware and cutlery, and mixtures thereof, with an aqueous liquid having dissolved or dispersed therein an effective amount of a composition for the automatic dishwashing according to the invention. For an effective amount of the composition for the automatic dishwashing, it is tried to say from 8g to 60g of product dissolved or dispersed in a washing solution with a volume of 3 to 10 liters, which are typical doses of product and volumes of solution of washing commonly used in conventional methods of automatic dishwashing.

Packing for compositions Commercially sold forms of bleaching compositions can be packaged in any suitable container including those made of paper, cardboard, plastics and any suitable laminates. A preferred packaging modality is described in European application No. 94921505.7.

Abbreviations used in the examples In the detergent compositions, the identifications of abbreviated components have the following meanings: LAS: Linear sodium alkylbenzene sulfonate of C-j 2 TAS: Sodium tallow alkyl sulfate CxyAS: Sodium alkylsulphate of C < | xC- | and C46SAS: C14-C-I6 secondary sodium alkylsulfate (2.3) CxyEzS: C-? xC-i sodium alkylsulfate and condensed with z moles of ethylene oxide CxyEz: A primary alcohol of C- | xC - | and predominantly linear condensed with an average of z moles of ethylene oxide. QAS 1: R2.N + (CH3) 2 (C2H40H) with R2 = linear alkyl of C9-C1 QAS 2: R2.N + (CH3) 2 (C2H4? H) with about 50% of R2 = linear alkyl of Cs; about 50% of R2 = C-J Q QAS 3: R2-N + (CH3) 2 (C2H4? H) with about 40% of R2 = linear alkyl of?, about 60% of R2 = linear alkyl of Cg QAS 4: R2.N + (CH3) 2 (C2H4? H) with R2 = linear alkyl of CQ QAS 5: R2-N + (CH3) 2 (C2H4? H) with R2 = C1-linear alkyl APA: Aliphatic polyamine Indosol E-50 (Sandoz) DMDAA: Dimethyldiallylammonium chloride (Crocolor NoH, Crosfield) Soap: Sodium alkylcarboxylate linear derivative of a mixture of 80/20 tallow and coconut oils CFAA: N-methylglucamide of (coconut) C12-C14 alkyl TFAA: N-methylglucamide of C- alkyl | 6-C-] Q TPKFA: Whole cut fatty acids of C-12-C 14 STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Na-] 2 (A1? 2Si? 2) i2- 27H2O, which has a primary particle size on the scale of 0.1 to 10 microns. Zeolite MAP: Zeolite MAP of hydrated sodium aluminosilicate having a silicon to aluminum ratio of 1.07 microns. NaSKS-6: Crystalline layered silicate of the formula d-Na2Si2? 5 Citric acid: Anhydrous citric acid Borate: Sodium borate Carbonate: Anhydrous sodium carbonate with an average particle size of 200μm and 900μm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution of between 400μm and 1200μm Silicate: Amorphous sodium silicate (Si? 2: Na2? = 2.0 ratio) Sodium sulphate: Anhydrous sodium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a distribution of particle size between 425μm and 850μm MA / AA: Copolymer of 1: 4 maleic acid / acrylic acid with an average molecular weight of about 70,000 AA: Sodium polyacrylate polymer with average molecular weight of 4,500 CMC: Sodium Carboxymethylcellulose Cellulose ether: Methylcellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease: Proteolytic enzyme of activity 4KNPU / g sold under the trade name Savinase by Novo Industries A / S Alcalase: Proteolytic enzyme of activity 3AU / g sold by Novo Industries A / S Cellulase: Cellulite enzyme of activity 1000CEVU / g sold by Novo Industries A / S under the trade name Carezyme Amylase: Activity aminicylic enzyme 120KNU / g sold by Novo Industries A / S under the trade name Termamyl 120T Lipase: Lipolytic activity enzyme 100kLU / g sold by Novo Industries A / S under the trade name Lipolase Endolasa: Enzyme endoglunase activity 3000CEVU / g sold by Novo Industries A / S PB4: Anhydrous sodium perborate tetrahydrate of nominal formula NaB02.3H2O.H2? 2 PB1: Anhydrous sodium perborate bleach monohydrate of nominal formula NaB? 2-H2? 2 Percarbonate: Sodium percarbonate of nominal formula 2Na2C? 3.3H2? 2 NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt TAED: Tetraacetylethylenediamine Catalyst of Mn: MnIV2 (m-0) 3 (1, 4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF6) 2, as described in US patents Nos. 5,246,621 and 5,244,594. DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060. Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer Brightening 1: 4,4'-bis (2-sulphotrisyl) biphenyl disodium Brightener 2: 4,4'-bis (4 -anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilben-2: 2'-disulfonate disodium HEDP: 1,1-Hydroxyethoxyphosphonic acid EDDS: Ethylenediamine-N, N-disuccinic acid QEA: bis ( (C2H50) (C2H4? N) (CH3) -N + -C6H12-N + - (CH3) -bis ((C2H50) - (C2H4? N), where n = from 20 to 30 PEGX: Polyethylene glycol with a molecular weight of x PEO: Polyethylene oxide with a molecular weight of 50,000 TEPAE: Ethoxylated tetraethylenepentamine PVP: Polyvinylpyrrolidone polymer PVNO: Polyvinylpyridine N-oxide PVPVI: Polyvinylpyrrolidone copolymer and vinylimidazole SRP 1: Ester-blocked esters with sulfobenzoyl with oxyethyleneoxy and terephthaloyl skeleton SRP 2: Poly (1, 2-propylene-terephthalate) dietoxylated short block polymer Silicone Defoamer: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1. Wax: Paraffin wax In the following examples, all levels are cited as% by weight of the composition: EXAMPLE 1 The following granular laundry detergent compositions of high density, A to F, of particular utility under European automatic washing conditions, are examples of the present invention: EXAMPLE 2 The following granular laundry detergent compositions, G a I, of particular utility under European automatic washing conditions, are examples of the present invention: EXAMPLE 3 The following detergent formulations, of particular utility under European machine wash conditions, are examples of the following invention.

EXAMPLE 4 The following granular detergent formulations are examples of the present invention. The formulation N is particularly suitable for use under Japanese automatic washing conditions. Formulations O to S are particularly suitable for use under US automatic washing conditions.

EXAMPLE 5 The following granular detergent formulations are examples of the present invention. Formulations W and X are particularly suitable for use under US automatic washing conditions. And it is of particular utility under Japanese conditions of automatic washing.

EXAMPLE 6 The following granular detergent compositions, of particular utility under European washing conditions, are examples of the present invention.

EXAMPLE 7 The following detergent compositions are examples of the present invention.

EXAMPLE 8 The following detergent formulations are examples of the present invention.

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising: a) a dye fixing cationic agent; and b) a cationic surfactant of formula I: R1R2R3R4N + X- (I) wherein R1 is a hydroxyalkyl group having not more than 6 carbon atoms; each of R2 and R3 is independently selected from C-M alkyl or alkenyl; R 4 is an alkyl or alkenyl of Cs-is; and X "is a counterion

2. A detergent composition according to claim 1, characterized in that the cationic surfactant is present in an amount of 0.01% to 20% by weight of the composition. according to claim 2, characterized in that the cationic surfactant is present in an amount of 0.05% to 5% by weight of the composition 4.- A detergent composition according to claim 1, characterized in that in the cationic compound of formula I, R4 is an alkyl group of C6-n 5. A detergent composition according to claim 1, characterized in that in the cationic compound of formula I, R1 is -CH2-CH2-OH, or -CH2CH2CH2-OH; R2 and R3 are each methyl, R4 is Cd-n alkyl, 6.- A detergent composition according to claim 1, characterized in that the cationic dye-fixing agent comprises a polyamine allyl. 7. A detergent composition according to claim 1, characterized in that the cationic surfactant comprises a compound of formula I in which R4 is a higher alkyl group having n carbon atoms, wherein n is 8 to 11, and a compound of formula I in which R 4 is a lower alkyl group having (n-2) carbon atoms. 8. A detergent composition according to claim 7, characterized in that the cationic surfactant comprises from 35 to 65% by weight of a compound of formula I, which has a higher alkyl group, and from 35 to 65% of a compound of formula I having a lower alkyl group. 9. A detergent composition or component thereof, comprising: a) a dye fixing cationic agent; and b) a mixture of cationic surfactants of formula I: R1R2R3R4N + X '(I) in which R1 is a hydroxyalkyl group having not more than 6 carbon atoms; each of R2 and R3 is selected from C ^ alkyl or alkenyl; R4 is an alkyl or alkenyl of Cs-iß; and X "is a counterion, and wherein, in the mixture of cationic surfactants of formula I, at least 10% by weight have R4 which is C5-9 alkyl or alkenyl 10. A detergent composition in accordance with claim 1, further characterized in that it comprises a nonionic surfactant selected from the group consisting of alcohol ethoxylates, alkylphenol ethoxylates, polyhydroxy fatty acid amides, polyol glycosides and mixtures thereof. 11. A detergent composition in accordance with claim 1. 10, characterized in that it comprises from 0.5% to 20% by weight of a nonionic surfactant 12.- A detergent composition according to claim 1, further characterized in that it comprises a fabric softening compound. according to claim 1, further characterized in that it comprises at least 1% by weight of anionic surfactant. detergent formed by the combination of a dye fixing cationic agent and a cationic surfactant of formula I: R1R2R3R4N +? - 0) wherein R1 is an optionally substituted phenol or hydroxyalkyl group having not more than 6 carbon atoms; each of R2 and R3 is independently selected from alkyl or alkenyl of C -? - 4; R 4 is an alkyl or alkenyl of Cß-n; and X "is a counterion, with one or more optional detergent components 15.- A method of washing or wiping to wash clothes in a domestic washing machine, in which an assortment device containing an amount in the washing machine is introduced. Effective of a detergent composition according to claim 1, before starting the washing, wherein said assorting device allows the progressive release of said detergent composition in the washing solution during the washing operation.